EP2072484B1 - Olefin oligomerization process - Google Patents

Olefin oligomerization process Download PDF

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EP2072484B1
EP2072484B1 EP09157119.0A EP09157119A EP2072484B1 EP 2072484 B1 EP2072484 B1 EP 2072484B1 EP 09157119 A EP09157119 A EP 09157119A EP 2072484 B1 EP2072484 B1 EP 2072484B1
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zsm
catalyst
feedstock
molecular sieve
oligomerization
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EP2072484A1 (en
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Stephen Brown
Georges Mathys
John Godsmark
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7026—MFS-type, e.g. ZSM-57
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/703—MRE-type, e.g. ZSM-48
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7046—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/18—Acids of phosphorus; Salts thereof; Phosphorus oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/80—Mixtures of different zeolites

Definitions

  • the present invention relates to a process for the oligomerization of olefin containing feedstocks, particularly feedstocks containing at least 65 wt.% olefins, and more particularly but not exclusively sulfur containing feedstocks.
  • the oligomerization of lower olefins, particularly C 2 to C 6 olefins, to produce higher molecular weight olefinic products is an important commercial process useful in, for example, the production of fuels and precursors for plasticizers, surfactants, and freeze point depressants for lubricating oils.
  • oligomerizing olefins typically mixtures of propylene and butenes
  • FCC Fluid Catalytic Cracker
  • SPa catalyst typically produces 500 to 1500 weight units of oligomer per weight unit of catalyst and then reaches the end of its useful life.
  • FCC Fluid Catalytic Cracker
  • SPa catalyst typically produces 500 to 1500 weight units of oligomer per weight unit of catalyst and then reaches the end of its useful life.
  • most operators are required to shut down and reload catalyst into a reactor every 3 to 10 weeks. The reactor is taken off line, refilled with fresh catalyst, and brought back on line. Reactor turnaround for sPa catalyst is particularly difficult.
  • sPa catalyst agglomerates to form a single, solid block which must be water jetted or drilled out of the reactor.
  • sPa catalyst is inexpensive (currently about $2/1b)
  • catalyst cost to produce oligomer is high compared to processes with more productive catalysts such as hydrotreating catalysts, hydrocracking catalysts, FCC catalysts, ethylbenzene and cumene catalysts, xylene isomerization catalysts, etc. due to the large quantities of sPa catalyst required and the expense associated with shutting down and restarting reactors.
  • sPa catalyst useful lifetime is limited by the increasing pressure drop caused by the steady catalyst agglomerization and not by loss of too much catalyst activity. Because of these problems, operators of sPa olefin oligomerization units are careful to maintain operating conditions that maximize catalyst cycle length. The rate of sPa fouling is known to increase with increasing feed olefin concentration. Many sPa operators therefore dilute the olefin feedstock with a paraffin recycle to increase catalyst lifetime. Paraffin dilution decreases the capacity of the unit by taking up space in pumps, reactors, heat exchangers and distillation towers.
  • zeolites can be attractive replacements for sPa catalysts because of their unique selectivities in olefin oligomerization.
  • zeolite catalysts in light olefin oligomerization service do not swell and fuse, and the pressure drop across the unit remains small and constant throughout the full catalyst cycle.
  • Zeolite catalyst fouling is also typically independent of feed olefin concentration.
  • U.S. Patent Nos. 3,960,978 and 4,021,502 disclose the conversion of gaseous olefins in the range of ethylene to pentene, either alone or in admixture with paraffins, into an olefinic gasoline blending stock by contacting the olefins with a ZSM-5 type zeolite.
  • EP-B-746,538 discloses oligomerization of propene and butene to produce enhanced yields of the trimer using zeolites of the structure types MFI, TON, and MFS, such as ZSM-5, ZSM-22 and ZSM-57.
  • U.S. Patent No. 4,520,221 describes a two-stage process for the polymerization of a lower olefin such as propylene to a high VI lubricating oil, using as catalyst in the first stage a HZSM-5 zeolite of which the surface is poisoned with a bulky alkylpyridine and in the second stage a second and/or different zeolite.
  • the purpose is to achieve both high yields and high VI by this two-stage process.
  • U.S. Patent No. 5,672,800 describes a process for oligomerization of C 2 -C 12 alkene-containing feedstock having a water content of from 0.05 to 0.25 molar % over a zeolite catalyst.
  • U.S. Patent No. 6,143,942 and International Patent Publication No. WO 95/22516, published August 24, 1995 disclose an olefin oligomerization process comprising contacting a feed comprising at least one olefin under oligomerization conditions with a catalyst comprising at least one zeolite having a constraint index greater than 10, such as ZSM-22, and at least one zeolite having a constraint index of 2 to 10, such as ZSM-5 or ZSM-57, said zeolites being present in a proportion within the range of 10:90 to 90:10 by weight.
  • the two molecular sieves are in admixture but they can also be arranged in separate beds so that the feed passes through them in series.
  • the feed can contain an inert diluent, such as a saturated hydrocarbon, in addition to said at least one olefin.
  • a suitable diluent is said to be propane, advantageously in proportions of propene:propane from 10:90 to 60:40, especially about 50:50 by weight.
  • low molecular weight, aliphatic thiols, sulfides and disulfides are especially troublesome, for example dimethyl, diethyl, and ethyl methyl sulfides, n-propane thiol, 1-butane thiol and 1,1-methylethyl thiol, ethylmethyl and dimethyl disulfides, and tetrahydrothiophene.
  • the invention resides in one aspect in a process for oligomerizing an olefinic hydrocarbon feedstock comprising at least 65 wt.% olefins, the process comprising:
  • the hydrocarbon feedstock comprises at least 70 wt.% olefins, such as at least 75 wt.% olefins.
  • the invention resides in a process for oligomerizing an olefinic hydrocarbon feedstock comprising sulfur-containing molecules, the process comprising:
  • the 'feedstock' that contacts catalyst in the second step will in fact be the initial feedstock that has already been contacted under oligomerization conditions with catalyst in the first step.
  • the feedstock comprises at least one olefin having 2 to 6 carbon atoms such as propylene and/or butene.
  • the feedstock comprises at least one olefin having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as propylene and/or butene.
  • the hydrocarbon feedstock comprises 0.1 to 10,000 ppm, such as 1 to 100 ppm, by volume of sulfur-containing molecules.
  • the sulfur-containing molecules may, for example, be selected from methyl mercaptan, ethyl mercaptan, propyl mercaptan, dimethyl sulfide, diethyl sulfide, ethyl methyl sulfide, n-propyl sulfide, 1- and 2-propane thiol, 1-butane thiol and 1,1-methylethyl thiol, ethylmethyl disulfide, dimethyl disulfide and tetrahydrothiophene.
  • the crystalline molecular sieve of the first catalyst has the TON structure type.
  • the crystalline molecular sieve of the second catalyst has the MFS structure type.
  • the feedstock is hydrated prior to contact with the crystalline molecular sieve catalyst.
  • Figure 1 is a graph showing the deactivation rate for a ZSM-57 catalyst used in the oligomerization of propylene both with and without prior contacting with a ZSM-22 oligomerization catalyst.
  • Figure 2 is a graph showing the deactivation rate for a ZSM-57 catalyst used in the oligomerization of a propylene feedstock containing diethyl sulfide both with and without prior contacting with a ZSM-22 oligomerization catalyst.
  • the present invention provides a process for oligomerizing an olefinic hydrocarbon feedstock, and in particular a feedstock containing at least 65 wt. % olefins, in which the feedstock is contacted under oligomerization conditions with (a) a first oligomerization catalyst comprising a crystalline molecular sieve having pores defined by unidimensional channels formed by 10-membered rings of tetrahedrally coordinated atoms and (b) a second oligomerization catalyst comprising a crystalline molecular sieve having pores defined by multidimensional channels.
  • Such multidimensional rings are for example those normally formed by 10-membered or 12-membered rings of tetrahedrally coordinated atoms.
  • the oligomerized product from the second of (a) and (b) is contacted under oligomerization conditions with (c) an oligomerization catalyst comprising solid phosphoric acid (sPa).
  • This modification takes advantage of the particular catalytic characteristics of sPa for the (oligomer-rich) feedstock, while at the same time taking advantage of the catalytic characteristics of the unidimensional-channel and multidimensional-channel molecular sieves as described. Moreover, it enables low proportions of sPa to be used, thereby minimizing the handling and disposal problems typically associated with sPa.
  • the catalysts employed in said contacting (a) and said contacting (b) comprise stacked beds in a single reactor. In another embodiment, the catalysts employed in said contacting (a) and said contacting (b) are contained in separate reactors.
  • the hydrocarbon feedstock is contacted first with the unidimensional 10-ring molecular sieve catalyst prior to contacting with the multidimensional crystalline molecular sieve catalyst, that is, step (a) is effected before step (b).
  • step (a) is effected before step (b).
  • multidimensional sieves for example 10-ring and 12-ring molecular sieves, particularly ZSM-57, are highly selective for the production of dimers and trimers in the oligomerization of olefins such as propylene and butenes, they are sensitive to the presence of sulfur impurities in the feed and excessive exotherms can result if the olefin content is too high (> 65%).
  • unidimensional 10-ring molecular sieves, such as ZSM-22 are less sensitive to sulfur impurities and tend to restrict oligomerization at the dimer stage, thereby limiting the amount of exotherm that occurs, especially with high olefin content feeds.
  • placing the less active unidimensional channel catalyst e.g. ZSM-22 on top of the multidimensional channel catalyst e.g. ZSM-57 helps maintain an isothermal reactor profile in a tubular reactor.
  • Using a single bed of ZSM-57 or ZSM-22 catalyst results in a significant amount of extra heat being released at the top of a tubular reactor operating to effect olefins conversion at commercially useful >90% per pass conversion.
  • the extra heat is released at the top of the reactor because the reaction driving force is much higher there (monomer concentration is highest at the top of the tube).
  • Providing the more active catalyst at the bottom of the reactor tube helps shift heat release from the top to the bottom of the reactor allowing more isothermal operation. This helps optimize catalyst stability and selectivity.
  • the hydrocarbon feedstock used in the present process typically contains olefins having from 2 to 6 carbon atoms.
  • the feedstock itself may be or comprise an oligomer, such as a dimer, especially one provided by recycling a part of a product stream.
  • the feed contains propene, butenes, pentenes and/or hexenes. The process is especially applicable to propene and butene oligomerization.
  • the feedstock may contain greater than 65 wt.% olefins, such as greater than 70 wt.% olefins or greater than 75 wt.% olefins.
  • Suitable feedstocks include untreated refinery streams such as FCC, coker, and pygas streams as well as aromatics-containing streams, such as reformates.
  • One particularly preferred feedstock comprises an FCC light olefin stream, which typically comprises ethane, ethylene, propane, propylene, isobutane, n-butane, butenes and pentanes.
  • An example of such a feedstock possesses the following composition: Wt.% Mole % Ethane 3.3 5.1 Ethylene 0.7 1.2 Propane 4.5 15.3 Propylene 42.5 46.8 Isobutane 12.9 10.3 n-Butane 3.3 2.6 Butenes 22.1 18.32 Pentanes 0.7 0.4
  • the feedstock may comprise an inert diluent, for example, a saturated hydrocarbon.
  • the feedstock may also include sulfur-containing compounds, typically as impurities generated during production or separation of the feedstock.
  • the feedstock may comprise from 0.1 ppm to 10,000 ppm by volume of sulfur-containing compounds but more typically will contain from 1 ppm to 100 ppm, such as up to 50 ppm, for example up to 20 ppm by volume of such compounds.
  • a typically encountered feedstock may have from 1 to 30 or from 2 to 20 ppm by volume of sulfur compounds, and the process is well suited to treating such feedstocks.
  • the sulfur content is conveniently ascertained by gas chromatographic analysis using peak areas normalized with reference to a COS standard.
  • sulfur-containing compounds contained by the present feedstock include saturated aliphatic compounds, for example, thiols, sulfides, including cyclic sulfides, and disulfides.
  • Typical compounds include, for example, methyl mercaptan, ethyl mercaptan, propyl mercaptan, dimethyl sulfide, diethyl sulfide, ethyl methyl sulfide, n-propyl sulfide, 1- and 2-propane thiol, 1-butane thiol and 1,1-methylethyl thiol, ethylmethyl disulphide, dimethyl disulfide and tetrahydrothiophene.
  • the feedstock Prior to oligomerization, the feedstock may be hydrated and in particular sufficient water may be added to saturate the feedstock.
  • the feedstock comprises from 0.01 to 0.25, such as from 0.02 to 0.20 and for example from 0.03 to 0.10, molar % water based on the total hydrocarbon content of the feedstock.
  • the natural water content of the feedstock may be increased, for example, by passage through a thermostatted water saturator. Since the amount of water required to saturate the feedstock will depend upon the temperature and composition of the feedstock, control of the water content may be effected by appropriate control of the temperature of the feedstock.
  • the olefinic hydrocarbon feedstock is contacted, preferably initially, with a unidimensional 10-membered ring crystalline molecular sieve catalyst.
  • the catalyst can include any unidimensional 10-membered ring crystalline molecular sieve that is active in olefin oligomerization reactions.
  • Suitable unidimensional 10-ring molecular sieves include those of the TON structure type (for example, ZSM-22, ISI-1, Theta-1, Nu-10, and KZ-2), those of the MEL-structure type (for example, ZSM-11), those of the EUO structure type (for example, EU-1 and ZSM-50), those of the AEL structure type (for example, SAPO-11), those of the MTT structure type (for example, ZSM-23 and KZ-1) and members of the ZSM-48 family of molecular sieves (for example, ZSM-48 itself).
  • the term "structure type" is used in the sense described in the Structure Type Atlas, Zeolites 17, 1996.
  • the 10-ring molecular sieve used (preferably as the first catalyst) is ZSM-22, ZSM-23, or SAPO-11.
  • the composition and manufacture of ZSM-22 are described in, for example, U.S. Patent No. 4,556,477 and WO 93/25475 .
  • the composition and manufacture of ZSM-23 are described in, for example, U.S. Patent No. 4,076,842 .
  • the composition and manufacture of SAPO-11 are described in, for example, U.S. Patent Nos. 4,40,871 and 6,294,493 .
  • the olefinic hydrocarbon feedstock is also contacted (preferably as the second oligomerization catalyst) with a molecular sieve having pores defined by multidimensional channels.
  • a molecular sieve having pores defined by multidimensional channels.
  • such catalyst preferably comprises a medium pore size molecular sieve having multidimensional channels formed by 10-membered or 12-membered rings of tetrahedrally coordinated atoms.
  • the sieve preferably has a Constraint Index of 1 to 12. Constraint Index and a method of its determination are described in U.S Patent No. 4,016,218 , which is incorporated herein by reference.
  • suitable molecular sieves for use in the multidimensional sieve catalyst include those having the MFS structure type (for example, ZSM-57), those having the MFI structure type (for example, ZSM-5) and those having the FER structure type (for example, ZSM-35).
  • the molecular sieve employed in step (b), preferably as the second catalyst in the process is ZSM-57, the composition and manufacture of which are described in, for example, EP-A-74,121 and U.S. Patent No. 4,973,870 .
  • the molecular sieves employed herein are in their H- or acid form.
  • An as-synthesized molecular sieve is advantageously converted to its acid form by, for example acid treatment, e.g., by HCl, or by ammonium ion exchange, and subsequent calcination.
  • the calcined materials may be post-treated, such as by steaming.
  • the molecular sieves employed herein conveniently have a crystallite size up to 5 ⁇ m, such as within the range of from 0.05 to 5 ⁇ m, for example from 0.05 to 2 ⁇ m, and typically from 0.1 to 1 ⁇ m.
  • zeolites Although the invention has been described with reference to aluminosilicate zeolites, it is possible to use, as is known in the art, a material in which silicon and aluminum have been replaced in whole or in part by other elements, silicon more especially by germanium or phosphorus and aluminum more especially by boron, gallium, chromium and iron, materials containing such replacement lattice elements also being termed zeolites, and the term being used in the broader sense in this specification.
  • the molecular sieve may be supported or unsupported, for example in powder form, or used as an extrudate with an appropriate binder.
  • the binder is preferably present in an amount such that the oligomerization catalyst contains between 2 and 80 wt% of the molecular sieve.
  • the binder is conveniently a metal oxide, such as alumina
  • the bottom of the light olefin oligomerization reactor (or downstream reactors in series configuration) is filled with the multidimensional 10-ring or 12-ring molecular sieve catalyst and the top of the reactor is filled with the unidimensional, 10-ring molecular sieve catalyst.
  • the unidimensional, 10-ring molecular sieve catalyst selectively converts the feedstock monomers to dimers before the feedstock contacts the multidimensional molecular sieve catalyst bed.
  • the limited amount of heat released by the selective dimerization can be removed with conventional tubular or chamber reactors.
  • Light olefin (C2-C7) concentration is lowered by the downstream multidimensional molecular sieve catalyst.
  • Reduced light olefin, particularly propylene, feedstock is further converted to the desired distribution of higher oligomers over the downstream catalyst. Because the tendency to form uncontrollable exotherms is greatly reduced, feedstock with higher olefin concentration can be processed.
  • the unidimensional 10-membered ring molecular sieve catalyst may be provided in a separate bed or a separate reactor upstream of the multidimensional crystalline molecular sieve catalyst or may be provided as a top layer on the multidimensional molecular sieve oligomerization catalyst.
  • the reactor system comprises from 10 to 80 wt%, more preferably 15 to 60 wt%, of the unidimensional 10-membered ring molecular sieve based on the total weight of the unidimensional 10-membered ring molecular sieve and the multidimensional crystalline molecular sieve in the overall catalyst system.
  • reaction conditions used in the olefin oligomerization with the unidimensional 10-membered ring molecular sieve and with the multidimensional molecular sieve oligomerization catalysts are not narrowly defined and may be the same or different.
  • preferred operating temperatures for the olefin oligomerization are generally between 80°C and 350°C. Toward and above the upper end of the range, deoligomerization rates increase and may predominate over the oligomerization reaction, providing an upper limit to practical operation. More typically, the reaction temperature is in the range of 130°C to 320°C, such as between 135°C and 310°C, for example between 160°C and 260°C.
  • the pressure is conveniently in the range of 400 psig to 4000 psig (2860 to 27680 Kpaa), such as from 500 psig to 1500 psig (3550 to 10440 kPaa).
  • the olefin weight hourly space velocity is advantageously in the range of from 0.1 hr -1 to 20 hr -1 , such as from 0.5 hr -1 to 5 hr -1 .
  • At least one of (a) and (b) is conducted at conditions including a temperature ranging from 80°C to 350°C; an olefin weight hourly space velocity ranging from 0.1 hr -1 to 20 hr -1 and a pressure ranging from 2860 kPaa to 27680 kPaa.
  • At least one of (a) and (b) is conducted at conditions including a temperature ranging from 130°C to 320°C; a weight hourly space velocity ranging from 0.5 hr -1 to 5 hr -1 and a pressure ranging from 3550 kPaa to 10440 kPaa.
  • All of the examples are conducted in pilot units, with the liquid feedstock being fed to the units using displacement pumps controlled by mass flow meters.
  • the feedstock is saturated with water by passage upwardly through a vessel containing water at a constant temperature between 20 and 40 °C.
  • After exiting the hydrator the feed is pre-heated to the heater temperature and then passed downwards through a fixed-bed reactor equipped with an internal thermowell.
  • the oligomerization reaction is conducted at temperatures of 130 to 300°C and a pressure of 70 bar (7000 kPa) to ensure single phase conditions.
  • the reaction is exothermic leading to a non-isothermal temperature profile down the length of the catalyst bed.
  • the oligomerization catalysts 50% ZSM-57/50% alumina extrudate catalyst and 75% ZSM-22/25% alumina extrudate catalyst, used in Examples 1 to 7 have the properties set forth in Table 1 below.
  • the catalysts are in the activated hydrogen form.
  • Table 1 Catalyst ZSM-22 ZSM-57 Zeolite Content 75 50 SiO2/Al2O3 65 40 BET 240 358 n-hexane (mg/gm) 39 50 Alpha 45 180 Na (ppm) 110 ⁇ 50 K (ppm) 700 110 C (wt.%) 0.35 0.2
  • Example 1 ZSM-57 with 75 wt.% propylene feedstock (Comparative)
  • ZSM-57/alumina extrudates are used to process 75 wt.% propylene/25 wt.% propane feedstock. Reaction conditions are 70 bar (7000 kPa), 2 WHSV and a furnace temperature of 130-150°C. Deactivation data are provided in Figure 1 labeled ZSM-57. At the low end of the temperature range, propylene conversion is less than 40 wt.% and the reactor is nearly uniform in temperature from top to the bottom of the catalyst bed. Increasing temperature by as little as 2°C causes conversion to increase to greater than 99% and temperatures approaching 300°C are recorded at the top of the catalyst bed. Target conversion of 90% is not achievable.
  • Example 2 ZSM-57 with 50 wt.% propylene feedstock (Comparative)
  • ZSM-57/alumina extrudates are used to process 50 wt.% propylene/42 wt.% n-butane/8 wt.% isobutane feedstock. Reaction conditions are 70 bar (7000 kPa), 2-4 WHSV, 80-95% propylene conversion. Deactivation data are provided in Figure 1 labeled ZSM-57.
  • Example 3 ZSM-22 with 75 wt.% propylene feedstock (Comparative)
  • ZSM-22/alumina extrudates are used to process 75 wt.% propylene/25 wt.% propane feedstock. Reaction conditions are 70 bar (7000 kPa), 3 WHSV, 50-98% propylene conversion. Deactivation data are provided in Figure 1 labeled ZSM-22.
  • Example 4 ZSM-22 and ZSM-57 with 75 wt.% propylene feedstock
  • ZSM-22/alumina extrudates and ZSM-57/alumina extrudates are used to process 75 wt.% propylene/25 wt.% propane feedstock.
  • the feedstock first contacts 66 wt.% ZSM-22 catalyst located in the upper portion of the reactor,then 34 wt.% ZSM-57 catalyst located in the lower portion of the reactor. [Total weight of ZSM-22 and ZSM-57 in the reactor corresponds to 100 wt%].
  • Reaction conditions are 70 bar (7000 kPa), 3 WHSV, 85-98% propylene conversion. Deactivation data are provided in Figure 1 labeled ZSM-22 + ZSM-57.
  • Example 2 shows that ZSM-57 can be used as an active and stable catalyst for the conversion of 50 wt.% propylene/50 wt.% butanes feedstock.
  • Example 1 shows that increasing the propylene content of the feedstock to 75 wt.% can prevent the ability to operate.
  • the conditions of Example 1 are representative of commercial operations and the catalyst of Example 1 cannot be used to commercially process 75 wt.% propylene feedstock using conventional tubular or chamber reactors.
  • Example 3 shows that active and stable operation is possible with ZSM-22 catalyst during the processing of high concentration propylene feedstock.
  • Example 4 shows that active and stable operation is possible with ZSM-22 catalyst on top of ZSM-57 catalyst during the processing of high concentration propylene feedstock.
  • Dimers are formed in the top of the reactor bed and undergo subsequent conversion to the desired product in the bottom of the catalyst bed.
  • ZSM-22 allows processing of feeds rich in propylene because ZSM-22 is dimer selective.
  • Example 4 shows that ZSM-22 can be used in combination with downstream multidimensional molecular sieves to allow stable operation with high olefin concentration feedstocks and maintain selectivity to higher oligomers versus dimers.
  • ZSM-57/alumina extrudates are used to process refinery propylene feedstock containing sulfur and oxygenate impurities having the composition as set forth in Table 2 below. Reaction conditions are 70 bar (7000 kPa), 2 WHSV, 80-95% propylene conversion. Deactivation data are shown in Figure 2 labeled ZSM-57/10 ppm DES (diethyl sulfide).
  • ZSM-57/alumina extrudates are used to process 50 wt.% propylene/42 wt.%n-butane/8 wt.% isobutane feedstock.
  • the feedstock contained no sulfur compounds.
  • Reaction conditions are 2-4 WHSV, 70 bar (7000 kPa), 80-95% propylene conversion.
  • Deactivation data are shown in Figure 2 labeled ZSM-57/0 ppm DES.
  • Example 7 ZSM-22 and ZSM-57 with sulfur-containing feedstock
  • ZSM-22/alumina extrudates and ZSM-57/alumina extrudates are used to process 75 wt.% propylene/25 wt.% propane feedstock spiked with 10 or 20 ppm DES.
  • the top of the reactor is loaded with 66 wt.% ZSM-22 oligomerization catalyst and the bottom of the reactor is loaded with 34 wt.% ZSM-57 oligomerization catalyst.
  • the feedstock is first contacted with the ZSM-22 oligomerization catalyst followed by the ZSM-57 oligomerization catalyst. Reaction conditions are 70 bar, 3 WHSV, 85-98% propylene conversion. Deactivation data are shown in Figure 2 labeled ZSM-22 + ZSM-57/10 ppm DES.

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